You are on page 1of 4

Proceedings of the XIVth International Symposium on High Voltage Engineering,

Tsinghua University, Beijing, China, August 25-29, 2005

D-28

Determination of the Brittle Fracture Process of Field Failed HV Insulators


by
C. de Tourreil

G. Thvenet

E. Brocard

N. Siampiringue

N. Pichon

Consultant
CH-1260 Nyon
Switzerland

SEDIVER
F-03270 St-Yorre
France

SEDIVER
F-03270 St-Yorre
France

CNEP
F-63177 Aubire
France

CNEP
F-63177 Aubire
France

c.dt@ieee.org

gthevenet@sediver.fr

ebrocard@sediver.fr

n.pichon@cnep-ubp.com

2- Brittle Fracture Processes

Abstract : The brittle fracture of composite insulators is


caused by the simultaneous action of an acid and a tensile
mechanical stress on the FRP (Fiber Reinforced Plastic)
core. Two diagnostic techniques are described that can be
used to determine what type of acid is present on the
fracture surface of field failed insulators. The analysis of 18
field failed insulators reveals, for most of them, the
presence on the fracture surface of a type of acid that is
produced by the hydrolysis of the resin of the FRP core.

Two stress factors are required to obtain the brittle fracture


of the core of a composite insulator. The first, a mechanical
tension, is always present because of the service load
applied to suspension/tension composite insulators. The
second necessary component is the presence of an acid
that comes in contact with the FRP rod.
The uncertainty regarding the exact type and the source of
the acid that causes brittle fractures in the field is the
probable reason why the problem is still affecting
composite insulators.

Key words : insulators, brittle fracture, nitric acid analysis,


carboxylic acid analysis

1-

siam@cnep-ubp.com

It is unlikely that acids, such as nitric or sulfuric, found in


acid rain would be of sufficient potency to lead to insulator
failures. In addition, to be the cause of failure, such an
external source of acid would have to have direct access to
the FRP rod. This means that somewhere along the length
of the insulator, its housing has been damaged and no
longer protects the FRP core.

Introduction

The first brittle fracture failures of composite insulators


occurred in the early 1970s [1], [2]. This type of failure is
still affecting composite insulators. However the total
number of insulators that have failed in that way is very
small. Worldwide, that number has been estimated to be at
most of few hundred units [3]. This number is very small
compared to the several millions of composite insulators
installed on transmission lines. Nevertheless, the brittle
fracture of an insulator is a serious event since it likely
leads to a conductor drop to the ground.

It has also been proposed that an acid, possibly oxalic acid,


created by electrical discharges occurring on the surface
(usually epoxy) of very small voids possibly present inside
the FRP rod, would explain field failures [7]. Tests,
performed by CIGRE WG 22-03 (now B2-03) have
indicated that this scenario is unlikely and is no longer
considered.

The brittle fracture phenomenon has been reproduced in


the laboratory shortly after the first events in service [4]. It
was found that the simultaneous application of a tensile
stress and of nitric acid to the FRP (Fiber Reinforced
Plastic) core would quickly lead to the failure of the core by
brittle fracture. This first experiment influenced all the work
done subsequently to explain the brittle fracture
phenomenon [5]. However, a different scenario recently
showed that an acid generated by the hydrolysis of the
resin of the FRP core could also lead to the failure of the
core. The present state of knowledge on the brittle fracture
phenomenon has been summarized in a recent papers [6].

Two other failure processes are described in this report, the


first involves nitric acid and the second one an acid
generated by the hydrolysis of the resin used for the
impregnation of the glass fibers of the FRP core.
2.1

The nitric acid scenario

When corona or dry band discharges occur in moist air,


nitric acid can be produced. Some chemical reactions that
explains the phenomenon are :

In the laboratory, many different acidic as well as alkaline


solutions can produce the brittle fracture of FRP cores.
Therefore, to establish the correct cause of a brittle fracture
that occurred in service, it is necessary to find some
analytical methods that can be used to establish the
presence of a given type of acid on the fracture surface of
the insulators. This only can decide which one of a number
of scenarios is responsible for the failures that occurred in
the field. In the study presented here, 18 brittle fracture
surfaces of insulators that had failed in the field have been
analyzed to establish the type of acid that caused the
fractures.

Primary reactions :
N2 + O2 and corona oxides of nitrogen
3O2 and corona 2O3
Some examples of secondary reactions to create Acids :
NO + O3 NO2+ O2
2NO2 + H2O HNO3 (aq) + HNO2 (aq)
N2O5 + H2O 2HNO3
HNO2 + O3 HNO3 + O2
If the core of a composite insulator is exposed to the
atmosphere because of a damaged housing in an area

Proceedings of the XIVth International Symposium on High Voltage Engineering,


Tsinghua University, Beijing, China, August 25-29, 2005

arrangement of the various atoms. This technique involves


the study of molecular vibrations. A continuous beam is
passed through or reflected off the surface of the sample,
individual molecular bonds and bond groupings vibrate at
characteristic frequencies. The resulting curve is known as
an infrared (IR) spectrum. FTIR-PAS (Photo-Acoustic
Spectroscopy) is a variant of the technique that can be
used on any sample that absorbs infrared radiation and is
independent of the sample morphology and requires no
special sample preparation.

where the electrical field is such that electrical discharges


can occur, nitric acid may be generated. Provided that the
nitric acid is of sufficient concentration and is not washed
off by the rain, a brittle fracture can occur because, in
service, the insulators is also under a mechanical tension
load.
2.2

The carboxylic acid scenario

Three families of resins are presently used for the


manufacture of the FRP core of composite insulators. They
are epoxy, vinylester and polyester resins.

FTIR-PAS analysis has been used in this study for the


detection of both nitric and carboxylic acids.

It can be shown that all three families can, under certain


circumstances specific to each family, be affected by water
and generate, because of hydrolysis, carboxylic acid.

3.1

C
C

H2O

OH

OH

Detection of the presence of nitric acid

The presence of nitric acid on the fracture surface of an


FRP core is detected using the reaction of potassium
bromide (KBr) with nitric acid (HNO3). This reaction
produces a potassium nitrate salt (KNO3). This nitrate ion
has a specific IR absorption at 1384 cm-1. Figure 1
compares the IR spectrum obtained by FTIR of a standard
sample of KNO3 salt with that obtain from the reaction of
HNO3 and KBr. FTIR microspectroscopy was also carried
out.

In the case of a specific epoxy resin commonly used to


make FRP cores, the hydrolysis of the hardener leads to
the creation of carboxylic acid according to the following
reaction :
O

D-28

For this to happen electrical discharges are not required.


However, water or moisture must be in contact with the
core and some hardener must still be present in the cured
resin. This could be the case if too much hardener has
been used in the formulation or, more likely, if the
polymerization is not complete because of insufficient
curing time or temperature. This can be checked by IR
analysis of the FRP core.
The presence of water can be explained by the migration of
water vapor through the housing in an area where there is
a lack of bonding to the core where it then accumulates.
More likely water can reach the FRP core because of a
damaged housing or a faulty seal between the housing and
the end fitting.

Fig. 1 : Identification of nitric acid


This technique can be used to analyze the fracture surface
of field failed insulators. Fig 2 shows the spectrum
associated with the fracture surface of a composite
insulator and that of a sample taken from inside its core.

The simultaneous presence of carboxylic acid and of the


mechanical tension load is sufficient to lead to the brittle
fracture of the insulator core.
3-

Field Brittle Fractures

Laboratory simulations show that both the nitric acid and


the carboxylic acid scenarios can produce the brittle
fracture of FRP cores. It is therefore necessary to use
special diagnostic techniques that permit to decide which
scenario is responsible for a given failure that occurred in
service. The diagnostic technique must be capable of
detecting the presence of the relevant type of acid on the
fracture surface of the insulator.
Infrared spectroscopy is commonly used both as qualitative
tool for identifying the molecular structure of organic
compounds and as a quantitative technique for determining
component concentrations. The position of wavelength of
the infrared absorption band depends only of the molecular

Fig. 2 : Identification of nitric acid on the fracture surface of


sample 1

Proceedings of the XIVth International Symposium on High Voltage Engineering,


Tsinghua University, Beijing, China, August 25-29, 2005

3.2

Detection of the presence of carboxylic acid

D-28

appearing between 3650 cm-1 and 3000 cm-1 (hydrolysed


products). It also shows an absorption band of lower
magnitude between 1600 cm-1 and 1710 cm-1 (carbonyl
function), with, in particular, a peak around 1700 cm-1. A
global absorption between 1600 and 1850 cm-1 (carbonyl
function) can also be observed. As previously, these
modifications indicate the presence of carboxylic acid.

Comparing the FTIR spectra of the fracture surface with


that of a sample taken within an epoxy resin core, i.e. that
has never been exposed to moisture can show the
presence of carboxylic acid and its source. The carboxyl
function has a peak around 1710 cm-1 and 1700 cm-1 and
the hydroxyl function a peak around 3437 cm-1. When such
peaks are present in the spectrum associated with the
fracture surface, the spectrum of a sample taken inside the
core shows peaks at 1845 cm-1 and 1770 cm-1 indicating
the presence of residual anhydride (unreacted hardener).
These peaks being absent on the fracture surface show
that the unreacted hardener has been transformed into
carboxylic acid. This is shown on Figure 3 and Figure 4.

4-

Analysis of Field Failed Insulators

The FTIR diagnostic technique has been used to establish


what kind of acid was responsible for the brittle fracture of
field failed composite insulators.
The fracture surfaces of 18 insulators have been analyzed
to look for evidence of both nitric acid and carboxylic acid.
All these insulators failed after a few years in service on
transmission lines. They had FRP cores made of epoxy,
vinylester or polyester. Table 1 presents the results of this
analysis.
Table 1
Results of Spectra Analysis
Sample
No :
1

Location
USA

Core
Type *
P

2
3

USA
USA

P
E

N**
acid
Very
high
Traces
Traces

4
5

USA
USA

V
P

Traces
Low

USA

7
8
9

USA
USA
USA

P
V
P

Very
high
Traces
Traces
Traces

10

USA

11

USA

12
13
14

USA
USA
USA

P
P
V

15
16
17

ZA
ZA
Israel

E
E
V

18

USA

Fig. 3 : Identification of carboxylic acid on the fracture


surface of sample 3
Similarly, with vinylester resins cores, the comparison of
the FTIR spectra of the fracture surface and of samples
taken inside the core shows modifications around 36503000cm-1 (hydrolysed products), and the appearance of a
peak at 1700 cm-1, corresponding to the absorption from
carboxylic acid. In addition there is a global absorption
increasing between 1600 and 1850 cm-1. This shows that
the hydrolysis of vinylester can also generate carboxylic
acid.

*:
Fig. 4 : Identificationof carboxyklic acid on the fracture
surface of sample 16
5-

The same comparison between the spectra of the fracture


surface and of a resin sample taken within a core made
with polyester resin shows a large absorption band

E is Epoxy
P is Polyester
V is Vinylester

Very
high
Low
Traces
Traces
Very
high
Traces
Traces
No
Very
high

** :

C**
acid
High
High
Very
high
High
High
Low
High
High
Low
Very
high
Very
high
High
High
Very
high
High
High
Very
high
Traces

Probable
scenario
N and/or
C
C
C
C
N and/or
C
N
C
C
N and/or
C
N and/or
C
C
C
C
N and/or
C
C
C
C
N

N is nitric acid
C is carboxylic acid

Discussion

The type of resin used for the manufacture of the cores is


fairly well divided between the 18 insulator samples, one

Proceedings of the XIVth International Symposium on High Voltage Engineering,


Tsinghua University, Beijing, China, August 25-29, 2005

failure of the core by brittle fracture for a practically


sufficiently long period to avoid failures in service.

third is vinylester with one more polyester resin and one


fewer epoxy resin.
Eleven samples failed because of carboxylic acid; this is
clearly more than the two samples that failed because of
nitric acid. For 5 samples it is not possible to clearly
attribute the failure to one or the other acid type.

7-

Acknowledgement

The authors are grateful to Dr. A. Phillips for his help in the
procurement of several of the samples and to CIGRE WG
B2-03 for both supplying some samples and the results of
their analysis.

It is important to note that the presence of carboxylic acid


indicates that the particular core was susceptible to
hydrolysis. In the five samples where both types of acids
were found it is possible that the failure was initiated by the
carboxylic acid in an area of high electrical field and that
the process took long enough for electrical discharges to
produce nitric acid and consequently compound the
problem.

References
[1] Cojan M., Perret J., Malaguti C., Nicolini P., Looms
J.S.T., Stannet A.W., "Polymeric Transmission
Insulators : Their Application in France, Italy and the
U.K.", CIGRE-session, Paris 1980, Paper 22-10.

In addition, other observations do not favor the nitric acid


scenario [8]. Several composite insulators that have been
in service for many years with some defects have not failed.
For example there are many more insulators that have
operated for several years with an exposed rod and
evidence of electrical discharges on the core. These
insulators have not failed by brittle fractures although all the
necessary factors were present : a tensile mechanical load
and electrical discharges in moist air that could have lead
to the production of nitric acid.
6-

D-28

[2] Weihe H., Reynders J.P., Macey R.E. : "Field


Experience and Testing of new Insulator Types in
South Africa", CIGRE-session, Paris 1980, Paper 22-03.
[3] CIGRE WG B2-03, Brittle Fractures of Composite
Insulators Field Experience, Occurrence and Risk
Assessment, ELECTRA 214, June 2004, pp. 40-47
[4] CIGRE document 22-80(IWD 10) 23, "Suspension and
Tension Composite Insulators for Overhead Lines Brittle Fracture at Low Mechanical Stresses",
November 1980, prepared by WG 22-10 IWD.

Conclusion

This study has shown that diagnostic techniques are


available to examine the fracture surface of composite
insulators that have failed by brittle fracture in the field. It is
therefore possible to determine what type of acid is
responsible for each failure.

[5] CEA Report, "Brittle Fracture of Non-Ceramic


Insulators", No 186 T 350, September 1986.
[6] CIGRE WG B2-03, Brittle Fractures of Composite
Insulators Failure Mode Chemistry, Influence of Resin
Variations and Search for a Simple Insulator Core
Evaluation Test Method, ELECTRA 215, August 2004,
pp. 16-22

The examination of 18 composite insulators that have failed


in service by brittle fracture has shown that it is at least 5
times, or even close to 10 times more likely that these
service occurring brittle fractures had been caused by
carboxylic acid than by nitric acid. This means that
particular care should be taken for the manufacture of FRP
cores. In addition it would be useful to investigate if there
exist other types of resin that are not sensitive to hydrolysis
and still have the characteristics required for the
manufacture of high quality FRP core for composite
insulators.

[7] Chandler H.D., Reynders J.P. "Electro-Chemical


Damage to Composite Insulators", CIGRE-session,
Paris 1984, Paper 33-08.
[8] C. de Tourreil, L. Pargamin, G. Thvenet. S. Prat and N.
Siampiringue, Brittle Fracture of Composite Insulators :
The New Explanation and a Field Case Study", ISH
2001, Paper 5-25, Bangalore, India, Aug. 2001.

It should be noted that the use of glass fibers that are more
resistant to acid attack, such as E-CR fibers, can delay the